EP4357136A1 - Method for producing transparent sheet, and transparent sheet - Google Patents

Method for producing transparent sheet, and transparent sheet Download PDF

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Publication number
EP4357136A1
EP4357136A1 EP22856299.7A EP22856299A EP4357136A1 EP 4357136 A1 EP4357136 A1 EP 4357136A1 EP 22856299 A EP22856299 A EP 22856299A EP 4357136 A1 EP4357136 A1 EP 4357136A1
Authority
EP
European Patent Office
Prior art keywords
transparent resin
resin film
transparent
die
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22856299.7A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jea Hoon RYU
Dae Young Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Publication of EP4357136A1 publication Critical patent/EP4357136A1/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0021Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/28Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/30Making multilayered or multicoloured articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C43/22Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/30Making multilayered or multicoloured articles
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C43/32Component parts, details or accessories; Auxiliary operations
    • B29C43/52Heating or cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
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    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0046Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
    • B32B37/0053Constructional details of laminating machines comprising rollers; Constructional features of the rollers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/156Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is calendered and immediately laminated
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    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/023Optical properties
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    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C63/00Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/02Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
    • B29C2063/027Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material applied by a squeegee
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00Indexing scheme relating to extrusion moulding
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    • B29C2948/92504Controlled parameter
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Definitions

  • the present invention relates to a method for manufacturing a transparent sheet, and a transparent sheet.
  • Transparent sheets used outdoors such as canopy and soundproof walls require high weather resistance in order to maintain transparency and prevent discoloration. Therefore, transparent polycarbonate sheets or transparent sheets manufactured by co-extruding a resin having excellent weather resistance or a resin having excellent UV stability on a transparent resin are used as the outdoor transparent sheets.
  • Patent Document 1 KR 10-2011-0011670 A
  • An object of the present invention for solving the above limitations is to secure weather resistance and chemical resistance without deterioration in the transparency of a transparent sheet while solving the complexity in the manufacturing process occurring during co-extrusion as well as minimizing the loss of the raw material resin.
  • an aspect of the present invention provides a method for manufacturing a transparent sheet having secured weather resistance and chemical resistance without deterioration in the transparency thereof while solving the limitations of co-extrusion through lamination rather than co-extrusion.
  • another aspect of the present invention provides a transparent sheet, which is manufactured by the method for manufacturing a transparent sheet, having secured weather resistance and chemical resistance without deterioration in the transparency thereof.
  • a method for manufacturing a transparent sheet and a transparent sheet manufactured thereby there are provided a method for manufacturing a transparent sheet and a transparent sheet manufactured thereby.
  • a transparent sheet is manufactured using the method for manufacturing a transparent sheet according to the present invention, not only the complexity in the manufacturing process occurring during co-extrusion can be solved, but the loss of the raw material resin can also be minimized, and further weather resistance and chemical resistance can be secured without deterioration in the transparency of the transparent sheet.
  • the present invention provides a method for manufacturing a transparent sheet.
  • the method for manufacturing a transparent sheet may include the steps of: extruding a first transparent resin from a T-die (S10); transferring, to a compression roll, the T-die first transparent resin film extruded from the T-die (S20); when the T-die first transparent resin film is discharged from the T-die and is fed into the compression roll, feeding a second transparent resin film together into the compression roll while bonding the second transparent resin film onto at least one surface of the T-die first transparent resin film (S30); and laminating the T-die first transparent resin film and the second transparent resin film using the compression roll (S40), wherein a first transparent resin may be a graft copolymer including a conjugated diene-based polymer, and a second transparent resin may be a graft copolymer including an acrylic polymer.
  • film and sheet are each resin molded articles having a predetermined thickness and showing a planar shape, and may be used in the same meaning, but specifically, when the thickness is relatively thin, or before lamination, the resin molded article may be referred to as a film, and when the thickness is relatively thick, or after lamination, the resin molded article may be referred to as a sheet.
  • the method for manufacturing a transparent sheet may be a method for manufacturing the transparent sheet by laminating the first transparent resin and the second transparent resin in the form of a film without co-extruding the first transparent resin and the second transparent resin.
  • step (S10) above may be a step of performing T-die extrusion to manufacture the first transparent resin in the shape of a film in order to manufacture a transparent sheet using the first transparent resin.
  • a first transparent resin supplied to the hopper of an extruder 10 may be discharged from a T-die 11 provided in the extruder 10 to manufacture a T-die first transparent resin film TR1 in the shape of a T-die film.
  • step (S10) above may be continuously performed, and accordingly, the T-die first transparent resin film TR1 may be continuously discharged from the T-die 11 provided in the extruder 10.
  • the extruder may have a temperature of 190 °C to 210 °C, and within this range, the surface temperature of the T-die first transparent resin film TR1 discharged from the T-die 11 may be maintained enough to be laminated with second transparent resin films TR21 and TR22 described subsequently, thereby inducing the lamination of the T-die first transparent resin film TR1 with the second transparent resin films TR21 and TR22 without the heating of a compression roll.
  • both a single-layer extruder and a multi-layer extruder may be applied as the extruder 10.
  • step (S20) above is a step of transferring the T-die first transparent resin film TR1 extruded from the T-die 11 to compression rolls 21 and 22 according to step (S10) above, and may be performed such that the T-die first transparent resin film TR1 may be directly fed into the compression rolls 21 and 22 without passing through a separate calender roll for smoothing before being fed into the compression rolls 21 and 22. That is, step (S20) above is characterized by being performed such that the T-die first transparent resin film TR1 discharged from the T-die 11 provided in the extruder 10 is directly fed into the compression rolls 21 and 22.
  • T-die first transparent resin film TR1 discharged from the T-die 11 provided in the extruder 10 is directly fed into the compression rolls 21 and 22, a separate calender roll is not required, thereby simplifying the process and minimizing the change in the surface temperature of the T-die first transparent resin film TR1, which may induce the lamination with the second transparent resin films TR21 and TR22.
  • step (S20) above may be continuously performed following step S10 above, and accordingly, from step (S10), the T-die first transparent resin film TR1 may be continuously discharged from the T-die 11 provided in the extruder 10 and at the same time, may be continuously transferred to the compression rolls 21 and 22.
  • step (S30) above may be a step of bonding the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 before the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 are fed to the compression rolls 21 and 22 such that the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 may be laminated on the compression rolls 21 and 22.
  • step (S30) above may be performed while the second transparent resin films TR21 and TR22 are bonded to at least one surface of the T-die first transparent resin film TR1 and fed into the compression rolls 21 and 22 together.
  • the bonding refers to inducing one surface of the second transparent resin films TR21 and TR22 to contact on at least one surface of the T-die first transparent resin film TR1, and the lamination is not performed by the bonding itself, and the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 may have a shape in which films are simply stacked by the bonding.
  • the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 may be bonded while being fed into the compression rolls 21 and 22.
  • step (S30) above may be continuously performed following steps (S10) and (S20) above, and accordingly, from step (S10), the T-die first transparent resin film TR1 may be continuously discharged from the T-die 11 provided in the extruder 10 and at the same time, may be continuously transferred and fed into the compression rolls 21 and 22, wherein the second transparent resin films TR21 and TR22 may be continuously bonded to at least one surface of the T-die first transparent resin film TR1 and may be fed into the compression rolls 21 and 22 together. Accordingly, in step (S30) above, the second transparent resin films TR21 and TR22 may be transferred to the compression rolls 21 and 22 while being unwound from winding rolls 41 and 42 around which the second transparent resin films TR21 and TR22 are wound.
  • step (S30) above when the T-die first transparent resin film TR1 is discharged from the T-die 11 and fed into the compression rolls 21 and 22, the second transparent resin films TR21 and TR22 may be simultaneously bonded to both surfaces of the T-die first transparent resin film TR1 while being fed into the compression rolls 21 and 22 together. In this case, it is possible to laminate the second transparent resin films TR21 and TR22 on both surfaces of the T-die first transparent resin film TR1.
  • step (S40) above is a step of laminating the T-die first transparent resin film TR1 and the second transparent resin film TR21 and TR22, which are fed from step (S30) above in a state of being bonded to each other into the compression rolls 21 and 22, and the T-die first transparent resin film TR1 and the second transparent resin film TR21 and TR22 may be laminated while passing through the compression rolls 21 and 22 to form a transparent sheet TS.
  • the transparent sheet TS formed through the compression rolls 21 and 22 may include: a T-die first transparent resin film layer; and a second transparent resin film layer stacked on at least one surface of the T-die first transparent resin film layer.
  • the compression rolls 21 and 22 may have a temperatures of 40 °C to 70 °C or 40 °C to 60 °C.
  • the compression rolls 21 and 22 may be a pair of calender rolls. That is, the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 bonded to at least one surface thereof, which are transferred to the compression rolls 21 and 22, may be fed through between a pair of compression rolls 21 and 22, which are a pair of calender rolls.
  • the pair of compression rolls 21 and 22 rotate about a rotational axis, wherein the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 bonded to at least one surface thereof, which are fed through between the pair of compression rolls 21 and 22, may be laminated due to compression caused by the pair of compression rolls 21 and 22, and thus, the transparent sheet TS may be manufactured while passing through the pair of compression rolls 21 and 22.
  • the transparent sheet TS having passed through the pair of compression rolls 21 and 22 may be fed and pass through between any one compression roll 21 of the pair of compression rolls and the compression roll 23 connected thereto, and may further pass through the additional calender rolls as necessary, and the positions of the plurality of compression rolls 21, 22, and 23 may be adjusted to positions enough for laminating the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 bonded to at least one surface thereof.
  • each of the compression rolls may include a tension roll, and in this case, the smoothness of the transparent sheet TS may be improved.
  • the diameter and length of the compression rolls 21, 22, and 23 may be adjusted according to the length of the T-die 11 provided in the extruder 10, the width and thickness of the transparent sheet TS to be manufactured, and the like, and may have the same diameter and length as each other.
  • step (S40) above may be continuously performed following steps (S10) to (S30) above, and thus, the transparent sheet TS having passed through the compression rolls 21, 22, and 23 may be wound around a separate winding roll (not shown) to be continuously obtained.
  • the method for manufacturing a transparent sheet may be performed according to not a simple roll-to-roll process but a similar roll-to-roll process in which the T-die first transparent resin film TR1 is discharged and transferred according to steps (S10) and (S20) above to be directly fed into the compression rolls 21 and 22, wherein the second transparent resin films TR21 and TR22 are fed together into the compression rolls 21 and 22 according to step (S30) above, and the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 bonded to at least one surface thereof are laminated while passing through the compression rolls 21 and 22 to manufacture the transparent sheet TS according to step (S40) above and wind the manufactured transparent sheet TS using the winding roll.
  • the present invention it is important to perform the method for manufacturing a transparent sheet according to steps (S10) to (S40) above, but it is also important to select the first transparent resin constituting the T-die first transparent resin film TR1 and the second transparent resin constituting the second transparent resin film in order to manufacture the transparent sheet TS without performing co-extrusion and without separately heating the compression roll when the T-die first transparent resin film TR1 and the second transparent resin films TR21 and TR22 bonded to at least one surface thereof are laminated, as in steps (S10) to (S40) above, while securing weather resistance and chemical resistance without deterioration in the transparency of the transparent sheet.
  • transparent sheets used outdoors such as canopy and soundproof walls, require high weather resistance in order to maintain transparency and prevent discoloration.
  • a transparent resin to be applied to such outdoor transparent sheets a polycarbonate resin, a polymethyl methacrylate resin, a glycol-modified polyethylene terephthalate resin, or a transparent ABS resin may be taken into account.
  • the polymethyl methacrylate resin having excellent weather resistance has a limitation of weak impact resistance and chemical resistance
  • the polycarbonate resin has a limitation of weak scratch resistance and weather resistance
  • the glycol-modified polyethylene terephthalate resin has a limitation of weak weather resistance and heat resistance
  • the transparent ABS resin has outstanding impact resistance, transparency, heat resistance, and scratch resistance, but has a limitation of very weak weather resistance and chemical resistance. Accordingly, the present invention is characterized in that the second transparent resin is introduced in order to secure the weather resistance and chemical resistance of the transparent resin.
  • the transparent sheet when the second transparent resin is simply introduced by co-extrusion with the first transparent resin, the transparent sheet is inevitably manufactured as a form in which the second transparent resin surrounds the first transparent resin, and in this case, when looking at the cross-section of the transparent sheet, each of the T-die first transparent resin film layer and the second transparent resin film layer unavoidably has non-uniform thickness in the TD direction of the transparent sheet.
  • Such thickness unevenness eventually causes an increase in the haze of the transparent sheet, and also causes warpage deformation depending on temperatures.
  • the thickness of the second transparent resin film layer is inevitably increased, the thickness unevenness causes deterioration in the impact characteristics of the transparent sheet itself.
  • the transparent sheet when the transparent sheet is manufactured according to the method for manufacturing a transparent sheet of the present invention, the second transparent resin films TR21 and TR22 are laminated on at least one surface of the T-die first transparent resin film TR1, and thus the transparent sheet is manufactured in a form in which the second transparent resin film layer is stacked on the T-die first transparent resin film layer, and in this case, when looking at the cross-section of the transparent sheet, each of the T-die first transparent resin film layer and the second transparent resin film layer has uniform thicknesses in the TD direction of the transparent sheet.
  • the transparent sheet manufactured according to the method for manufacturing a transparent sheet of the present invention only a portion of the T-die first transparent resin film layer, in which the second transparent resin film layer is not laminated, may be set as trimming lines when performing a trimming process of cutting unnecessary portions from the manufactured transparent sheet. In this case, the trimmed portion of the T-die first transparent resin film layer may all be recycled as the first transparent resin.
  • the resins of the T-die first transparent resin film layer and the second transparent resin film layer can be induced to have the same refractive index, preferably, as described below, the refractive indices are the same, and the monomer components for each resin are similar, so that even if the transparent sheet itself including both the T-die first transparent resin film layer and the second transparent resin film is recycled, the transparency and haze are not affected.
  • the thicknesses of the T-die first transparent resin film layer and the second transparent resin film layer are uniform, the haze of the transparent sheet is not affected, less warpage deformation occurs depending on temperatures, and the second transparent resin film layer can be formed thin, thereby having excellent transparency and color developability of the T-die first transparent resin film layer, and sufficiently securing impact properties of the transparent sheet itself.
  • the second transparent resin according to an embodiment of the present invention for achieving the advantage of the second transparent resin film layer may be a graft copolymer including an acrylic polymer.
  • transparent resins which may be taken into account as the first transparent resin, include a polycarbonate resin, a polymethyl methacrylate resin, a glycol-modified polyethylene terephthalate resin, and a transparent ABS resin, and the polycarbonate resin and the glycol-modified polyethylene terephthalate resin are not suitable for bonding and laminating the graft copolymer including the acrylic polymer which is the second transparent resin because the extrusion processing temperature is a high temperature, 270 °C to 300 °C when the T-die film is manufactured using the extruder 10.
  • the crystalline polymer is not suitable because peeling may occur after laminated with the second transparent resin film.
  • the first transparent resin according to the present invention is preferably a graft copolymer including a conjugated diene-based polymer such as a transparent ABS resin, in consideration of refractive index adjustment, recycling possibility, and compatibility with the second transparent resin.
  • the first transparent resin for being applied to the method for manufacturing a transparent sheet of the present invention may be a graft copolymer including a conjugated diene-based polymer
  • the second transparent resin may be a graft copolymer including an acrylic polymer
  • the method for manufacturing a transparent sheet according to the present invention can be applied only if the first transparent resin and the second transparent resin are satisfied.
  • the first transparent resin may be a graft copolymer including a conjugated diene-based polymer, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit.
  • the first transparent resin may be a graft copolymer formed by graft-polymerizing an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit to a conjugated diene-based polymer.
  • the conjugated diene-based polymer may include a conjugated diene-based monomer unit, and the conjugated diene-based monomer for forming the conjugated diene-based monomer unit may be at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene, and more specifically, may be 1,3-butadiene.
  • the conjugated diene-based polymer may further include an aromatic vinyl-based monomer unit as necessary.
  • the aromatic vinyl-based monomer for forming the aromatic vinyl-based monomer unit of the first transparent resin may be at least one selected from the group consisting of styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and specifically, may be styrene.
  • the vinyl cyan-based monomer for forming the vinyl cyan-based monomer unit of the first transparent resin may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile, and specifically, may be acrylonitrile.
  • the first transparent resin may further include an alkyl (meth)acrylate-based monomer unit in order to provide transparency
  • the alkyl (meth)acrylate-based monomer for forming the alkyl (meth)acrylate-based monomer unit may be an alkyl (meth) acrylate-based monomer having 1 to 12 carbon atoms, and specifically, may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and n-butyl acrylate.
  • the amount of each of the conjugated diene-based polymer, the aromatic vinyl-based monomer unit, the vinyl cyan-based monomer unit, and the alkyl (meth)acrylate-based monomer unit of the first transparent resin may be appropriately adjusted in order to secure the transparency of the first transparent resin prepared from the graft copolymer.
  • the first transparent resin may have a tensile strength of 100 kgf/cm 2 or more, 200 kgf/cm 2 or more, 300 kgf/cm 2 or more, or 350 kgf/cm 2 or more, and may also have a tensile strength of 800 kgf/cm 2 or less, 700 kgf/cm 2 or less, 600 kgf/cm 2 or less, 500 kgf/cm 2 or less, or 450 kgf/cm 2 or less.
  • the first transparent resin may have a flexural strength of 200 kgf/cm 2 or more, 300 kgf/cm 2 or more, 400 kgf/cm 2 or more, 500 kgf/cm 2 or more, or 600 kgf/cm 2 or more, and may also have a flexural strength of 1,000 kgf/cm 2 or less, 900 kgf/cm 2 or less, 800 kgf/cm 2 or less, 700 kgf/cm 2 or less, or 650 kgf/cm 2 or less.
  • the first transparent resin may have a flexural modulus of 10,000 kgf/cm 2 or more, 12,000 kgf/cm 2 or more, 15,000 kgf/cm 2 or more, 16,000 kgf/cm 2 or more, or 17,000 kgf/cm 2 or more, and may also have a flexural modulus of 50,000 kgf/cm 2 or less, 40,000 kgf/cm 2 or less, 30,000 kgf/cm 2 or less, 25,000 kgf/cm 2 or less, or 20,000 kgf/cm 2 or less.
  • the first transparent resin may have a notched izod impact strength at 23 °C of 1 kgfcm/cm or more, 2 kgfcm/cm or more, 3 kgfcm/cm or more, 4 kgfcm/cm or more, or 5 kgfcm/cm or more, and may also have a notched izod impact strength of 20 kgfcm/cm or less, 15 kgfcm/cm or less, 10 kgfcm/cm or less, 9 kgfcm/cm or less, 8 kgfcm/cm or less, or 7 kgfcm/cm or less.
  • the first transparent resin may have a heat deformation temperature of 50 °C or more, 60 °C or more, 70 °C or more, or 75 °C or more, and may also have a heat deformation temperature of 100 °C or less, 90 °C or less, or 85 °C or less.
  • the first transparent resin may have a melting index measured at a load of 10 kgf at 220 °C according to ASTM D1238 of 1 g/10 min or more, or 2 g/10 min or more, and may also have a melting index of 10 g/10 min or less, 8 g/10 min or less, 6 g/10 min or less, or 4 g/10 min or less.
  • the second transparent resin may be a graft copolymer including an acrylic polymer, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit.
  • the second transparent resin may be a graft copolymer formed by graft-polymerizing an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit to an acrylic polymer.
  • the transparency of a graft copolymer including an acrylic polymer, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit, corresponding to the second transparent resin, that is, an ASA resin has not been achieved.
  • the purpose of the present invention may be achieved by using, as the second transparent resin, the graft copolymer including a novel acrylic polymer having transparency, and using the conventional opaque ASA resin cannot achieve the purpose of the present invention because the transparency of the transparent sheet cannot be secured as in the present invention.
  • the acrylic polymer may include an acrylic monomer unit
  • the acrylic monomer for forming the acrylic monomer unit may be an alkyl (meth)acrylate-based monomer, specifically, an alkyl (meth)acrylate-based monomer having 1 to 12 carbon atoms, and more specifically, may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and n-butyl acrylate.
  • the aromatic vinyl-based monomer for forming the aromatic vinyl-based monomer unit of the second transparent resin may be at least one selected from the group consisting of styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and specifically, may be styrene.
  • the vinyl cyan-based monomer for forming the vinyl cyan-based monomer unit of the second transparent resin may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile, and specifically, may be acrylonitrile.
  • the amount of each of the acrylic polymer, the aromatic vinyl-based monomer unit, and the vinyl cyan-based monomer unit of the second transparent resin may be appropriately adjusted in order to secure the transparency of the second transparent resin prepared from the graft copolymer.
  • the second transparent resin may have a tensile strength of 100 kgf/cm 2 or more, 150 kgf/cm 2 or more, or 250 kgf/cm 2 or more, and may also have a tensile strength of 800 kgf/cm 2 or less, 500 kgf/cm 2 or less, or 350 kgf/cm 2 or less.
  • the second transparent resin may have an elongation of 50% or more, 55% or more, 600 or more, 650 or more, 700 or more, or 75% or more, and may have an elongation of 100% or less, 95% or less, 90% or less, or 85% or less.
  • the second transparent resin may have a flexural strength of 100 kgf/cm 2 or more, 300 kgf/cm 2 or more or 400 kgf/cm 2 or more, and may also have a flexural strength of 800 kgf/cm 2 or less, 600 kgf/cm 2 or less, or 500 kgf/cm 2 or less.
  • the second transparent resin may have a flexural modulus of 5,000 kgf/cm 2 or more, 8,000 kgf/cm 2 or more, 10,000 kgf/cm 2 or more, or 11,000 kgf/cm 2 or more, and may also have a flexural modulus of 30,000 kgf/cm 2 or less, 20,000 kgf/cm 2 or less, or 15,000 kgf/cm 2 or less.
  • the second transparent resin may have a notched izod impact strength at 23 °C of 1 kgfcm/cm or more, 2 kgfcm/cm or more, 3 kgfcm/cm or more, 4 kgfcm/cm or more, 5 kgfcm/cm or more, or 6 kgfcm/cm or more, and may also have a notched izod impact strength of 20 kgfcm/cm or less, 15 kgfcm/cm or less, 10 kgfcm/cm or less, 9 kgfcm/cm or less, or 8 kgfcm/cm or less.
  • the second transparent resin may have a heat deformation temperature of 50 °C or more, 60 °C or more, or 65 °C or more, and may also have a heat deformation temperature of 100 °C or less, 90 °C or less, or 80 °C or less.
  • the second transparent resin may have a melting index measured at a load of 10 kgf at 220 °C according to ASTM D1238 of 1 g/10 min or more, 2 g/10 min or more, or 3 g/10 min or more, and may also have a melting index of 10 g/10 min or less, 8 g/10 min or less, 6 g/10 min or less, or 5 g/10 min or less.
  • the second transparent resin may have a Rockwell hardness of 50 or more, 55 or more, 60 or more, 65 or more, 70 or more, or 75 or more, and may have a Rockwell hardness of 100 or less, 95 or less, 90 or less, or 85 or less.
  • the second transparent resin may have a haze of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, or 4% or less, and may have a haze of 0.1% or more, 0.50 or more, or 1% or more.
  • the second transparent resin may have a haze of 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, or 2.5% or less, and may have a haze of 0.1% or more, 0.50 or more, or 1% or more.
  • the second transparent resin may have a haze of 5% or less, 4% or less, 3% or less, 2.5% or less, or 2% or less, and may have a haze of 0.1% or more, 0.50 or more, or 1% or more.
  • the second transparent resin may have a transmittance (Tt) of 70% or more, 75% or more, or 80% or more, and may have a transmittance (Tt) of 100% or less, 95% or less, 90% or less, or 85% or less.
  • the second transparent resin may have a transmittance (Tt) of 80% or more, 85% or more, or 90% or more, and may have a transmittance (Tt) of 100% or less, 95% or less, 93% or less, or 92% or less.
  • the second transparent resin may have a transmittance (Tt) of 80% or more, 85% or more, or 90% or more, and may have a transmittance (Tt) of 100% or less, 95% or less, 93% or less, or 92% or less.
  • the first transparent resin and the second transparent resin may have the same refractive index. Accordingly, even when the second transparent resin film is laminated on the T-die first transparent resin film, the transparency of the transparent sheet can be maintained and an increase in the haze can be minimized.
  • the same refractive index means that the refractive index difference between the first transparent resin and the second transparent resin is ⁇ 0.1 or less, ⁇ 0.01 or less, ⁇ 0.001 or less, ⁇ 0.0001 or less, or ⁇ 0.00001 or less, or there is no difference therebetween.
  • the present invention if resins satisfying the physical properties are used as the first transparent resin and the second transparent resin, respectively, weather resistance and chemical resistance may be further improved without deterioration in the transparency of the transparent sheet when the transparent sheet is manufactured according to the present invention.
  • the present invention provides a transparent sheet.
  • the transparent sheet may be manufactured according to the method for manufacturing a transparent sheet as described above.
  • the transparent sheet may include: a T-die first transparent resin film layer; and a second transparent resin film layer laminated on at least one surface of the T-die first transparent resin film layer, wherein a first transparent resin is a graft copolymer including a conjugated diene-based polymer, a second transparent resin is a graft copolymer including an acrylic polymer, and the T-die first transparent resin film layer and the second transparent resin film layer each have a uniform thickness in the TD direction of the transparent sheet.
  • the first transparent resin and the second transparent resin may be the same as those described in the method for manufacturing a transparent sheet.
  • the thickness of each of the T-die first transparent resin film layer and the second transparent resin film layer is uniform in the TD direction of the transparent sheet, the haze of the transparent sheet is not affected, less warpage deformation occurs depending on temperatures, and the second transparent resin film layer can be formed thin, thereby having excellent transparency and color developability of the T-die first transparent resin film layer, and sufficiently securing impact properties of the transparent sheet itself.
  • the uniform thickness means that the thickness difference between the thickest portion and the thinnest portion in each of the T-die first transparent resin film layer and the second transparent resin film layer in the TD direction of the transparent sheet is ⁇ 0.05 mm or less, ⁇ 0.01 mm or less, ⁇ 0.005 mm or less, ⁇ 0.001 mm or less, or there is no difference therebetween.
  • the thickness of the T-die first transparent resin film layer may be 85% or more, 900 or more, or 95% or more, and 99% or less by thickness
  • the thickness of the second transparent resin film layer may be 1% or more, 15% or less, 10% or less, or 5% or less by thickness, and within this range, the impact resistance, heat resistance, and scratch resistance of the transparent sheet may not only be secured from the T-die first transparent resin film layer, but the weather resistance and chemical resistance may also be secured from the second transparent resin film layer without deteriorating the physical properties of the T-die first transparent resin film layer.
  • the thickness of the T-die first transparent resin film layer may be 1 mm or more, 2 mm or more, 3 mm or more, or 4 mm or more, and may be 10 mm or less, 8 mm or less, 7 mm or less, or 6 mm or less
  • the thickness of the second transparent resin film layer may be 0.01 mm or more, 0.05 mm or more, or 0.10 mm or more, and may be 0.50 mm or less, 0.30 mm or less, or 0.15 mm or less, and within this range
  • the impact resistance, heat resistance, and scratch resistance of the transparent sheet may not only be secured from the T-die first transparent resin film layer, but the weather resistance and chemical resistance may also be secured from the second transparent resin film layer without deteriorating the physical properties of the T-die first transparent resin film layer.
  • the transparent sheet may have a total light transmittance of 80% or more, 81% or more, or 81.5% or more, and may also have a total light transmittance of 90% or less, 88% or less, 85% or less, or 82% or less.
  • the transparent sheet may have a diffusion transmittance of 1% or more, 2% or more, 3% or more, or 4% or more, and may also have a diffusion transmittance of 10% or less, 8% or less, 6% or less, or 5% or less.
  • the transparent sheet may have a haze of 1% or more, 2% or more, 3% or more, or 5% or more, and may also have a haze of 10% or less, 8% or less, 7% or less, or 6% or less.
  • the transparent sheet may have a gloss at 60°of 100 or more, 110 or more, or 120 or more, and may have a gloss of 150 or less, 140 or less, 130 or less, or 125 or less.
  • LG Chem's product name TR562-23316 transparent ABS resin
  • LG Chem's product name LI901-INP transparent ASA resin
  • First transparent resin pellets were put into the hopper of the extruder 10 provided with the T-die 11, and extruded at an extruder temperature of 210 °C to discharge the T-die first transparent resin film TR1 having a thickness of 3 mm from the T-die 11. While the T-die first transparent resin film TR1 discharged from the T-die 11 is directly transferred to the compression rolls 21 and 22, the second transparent resin film TR21 having a thickness of 0.1 mm wound around a separate winding roll 41 is bonded to one surface of the T-die first transparent resin film TR1 and simultaneously fed through between the compression rolls 21 and 22.
  • the transparent sheet TS is passed through between the compression rolls 21 and 23, and then wound using a separate winding roll to manufacture the transparent sheet TS.
  • the temperature of the compression rolls 21 and 22 was 60 °C.
  • LG Chem's product name TR562-NP transparent ABS resin
  • LG Chem's product name LI901-INP transparent ASA resin
  • First transparent resin pellets were put into the hopper of the extruder 10 provided with the T-die 11, and extruded at an extruder temperature of 210 °C to discharge the T-die first transparent resin film TR1 having a thickness of 3 mm from the T-die 11. While the T-die first transparent resin film TR1 discharged from the T-die 11 is directly transferred to the compression rolls 21 and 22, the second transparent resin films TR21 and TR22 having a thickness of 0.1 mm wound around separate winding rolls 41 and 42 are bonded to both surfaces of the T-die first transparent resin film TR1 and simultaneously fed through between the compression rolls 21 and 22.
  • the transparent sheet TS is passed through between the compression rolls 21 and 23, and then wound using separate winding rolls to manufacture the transparent sheet TS.
  • the temperature of the compression rolls 21 and 22 was 60 °C.
  • the T-die first transparent resin film TR1 was manufactured as a transparent sheet without laminating the second transparent resin film TR21 to the T-die first transparent resin film TR1 in Example 1.
  • the T-die first transparent resin film TR1 was manufactured as a transparent sheet without laminating the second transparent resin films TR21 and TR22 to the T-die first transparent resin film TR1 in Example 2.
  • a commercially available polycarbonate resin was manufactured as a transparent sheet.
  • a commercially available polymethylmethacrylate resin was manufactured as a transparent sheet.
  • Example 1 had the second transparent resin film laminated on one surface thereof as compared with the transparent sheet in Comparative Example 1, it was confirmed that the color coordinates and the transparency were hardly changed, and thus the gloss was rather increased while the transparency was maintained.
  • Example 2 had the second transparent resin films laminated on both surfaces thereof as compared in the transparent sheet in Comparative Example 2, it was confirmed that the color coordinates and the transparency were hardly changed, and thus the gloss was rather increased while the transparency was maintained.
  • Chemical resistance was measured by the following method using the transparent sheets manufactured in Examples 1 and 2, Comparative Examples 1 and 2, and Reference Examples 1 and 2, and the results are shown in Table 2 and FIGS. 6 to 8 .
  • Example 1 did not generate cracks with respect to all of alcohol, base, and acid, and thus the chemical resistance was remarkably improved as compared with the transparent sheet in Comparative Example 1 in which cracks were generated in alcohol and acid.
  • Example 2 did not generate cracks with respect to all of alcohol, base, acid, and silicone, and thus the chemical resistance was remarkably improved as compared with the transparent sheets in Comparative Example 2 in which cracks were generated in alcohol and acid, Reference Example 1 in which tiny cracks were generated in acid, and Reference Example 2 in which cracks were generated in alcohol.
  • Example 1 and Comparative Example 1 were exposed to an accumulated light amount of 299.52 MJ (about 95 days of Xenon-Arc) using MV3000 Metal Halide (SUGA Co.) according to SAE J2527, and discoloration was observed. As a result, as shown in FIG. 9 , it was confirmed that the transparent sheet in Example 1 did not undergo discoloration, while the transparent sheet in Comparative Example 1 underwent discoloration.
  • MV3000 Metal Halide SUGA Co.
  • Example 2 Comparative Example 2 and Reference Example 1 were exposed to an accumulated light amount of 252 MJ (about 84 days of Xenon-Arc) using MV3000 Metal Halide (SUGA Co.) according to ASTM G155-1, and discoloration was observed.
  • MV3000 Metal Halide SUGA Co.
  • Example 1 dog bone-shaped transparent sheet specimens having a thickness of 3.2 mm were fixed to a jig, placed in a heat and cold resistance cycle chamber, and repeated three cycles by setting one cycle at -20 °C for 2 hours and at 80 °C and a relative humidity of 85% for 2 hours, and then presence of peeling, transparency, and haze change were observed.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
EP22856299.7A 2021-08-13 2022-08-12 Method for producing transparent sheet, and transparent sheet Pending EP4357136A1 (en)

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KR20210107579 2021-08-13
PCT/KR2022/012135 WO2023018306A1 (ko) 2021-08-13 2022-08-12 투명시트 제조방법 및 투명시트

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EP2305451B1 (en) 2008-05-13 2013-11-20 Mitsubishi Gas Chemical Company, Inc. Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof
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